CN113680374A - Composite photocatalyst and preparation method and application thereof - Google Patents
Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN113680374A CN113680374A CN202111143132.6A CN202111143132A CN113680374A CN 113680374 A CN113680374 A CN 113680374A CN 202111143132 A CN202111143132 A CN 202111143132A CN 113680374 A CN113680374 A CN 113680374A
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- etch
- sbo
- graphite
- carbon nitride
- phase carbon
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- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 266
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 87
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 238000004729 solvothermal method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 49
- 238000005406 washing Methods 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000004321 preservation Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 229910052788 barium Inorganic materials 0.000 claims description 24
- 229940071182 stannate Drugs 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 16
- 229910001626 barium chloride Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 52
- 238000010438 heat treatment Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 25
- 239000000523 sample Substances 0.000 description 22
- 238000001228 spectrum Methods 0.000 description 21
- 239000000919 ceramic Substances 0.000 description 20
- 230000001699 photocatalysis Effects 0.000 description 15
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000013507 mapping Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- 229910020923 Sn-O Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003609 H2PtCl4 Inorganic materials 0.000 description 2
- IOHIMQPBXKDRMQ-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Ba+2].[Sn+2]=O.S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Ba+2].[Sn+2]=O.S(=O)(=O)([O-])[O-] IOHIMQPBXKDRMQ-UHFFFAOYSA-J 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910002929 BaSnO3 Inorganic materials 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention discloses a composite photocatalyst and a preparation method and application thereof. The composite photocatalyst comprises graphite phase carbon nitride and tin oxideAnd the mass of the tin oxide composite barium sulfate is 1/30-1 times of that of the graphite-phase carbon nitride. The preparation method comprises the step of carrying out solvothermal reaction on the graphite-phase carbon nitride and tin oxide composite barium sulfate to obtain the composite photocatalyst. The invention provides a composite photocatalyst containing a graphite-phase carbon nitride and tin oxide composite barium sulfate electron transport material, which can efficiently catalyze and degrade triethanolamine and has the catalytic activity of 284 mu mol g‑1h‑1The photocatalyst is 2.5 times of pure graphite phase carbon nitride, has catalytic activity obviously higher than that of the existing graphite-like phase carbon nitride photocatalyst, has stable activity within 12 hours, can still maintain 85 percent of original activity within 18 hours, and solves the problem of poor stability of the graphite-like phase carbon nitride photocatalyst.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a composite photocatalyst as well as a preparation method and application thereof.
Background
The organic wastewater refers to wastewater containing organic pollutants as main components, and has great influence on society and life because water eutrophication is easily caused. The treatment of amine-containing organic wastewater mostly adopts biochemical treatment or biochemical and physicochemical combined treatment at present, and specifically comprises the steps of treating methyldiethanolamine-containing wastewater by microwave photochemical catalytic oxidation, treating high-concentration organic amine wastewater by a multi-stage physicochemical treatment and biochemical combined process, treating amine-containing organic wastewater by a complex extraction method or treating similar alcohol amine wastewater by an ion exchange method and a Fenton oxidation method.
The photocatalytic degradation of organic pollutants is widely developed at present, hydrogen obtained by treating wastewater through a photocatalyst and the degradation of pollutants are the purposes of photocatalytic traditional Chinese medicines, and in the hydrogen production reaction by photocatalytic water decomposition, photocatalytic materials are mainly concentrated on TiO2、Fe2O3、g-C3N4And CdS and the like, although numerous researches on the photocatalyst are carried out at present, the defects of complex synthesis path, low photocatalytic performance and the like of the photocatalyst still exist.
Graphite phase carbon nitride (g-C)3N4CN) is used as a photocatalyst capable of responding to visible light, and is widely developed in the fields of photocatalytic hydrogen production, photocatalytic pollutant degradation and the like, but the defects of low photocatalytic activity and stability still exist. The tin oxide and barium sulfate composite material is a novel composite carrier transmission material, CN is compounded with the carrier transmission material to promote the separation of photon-generated carriers of the CN, so that the photocatalytic activity and stability of the CN are improved, and the composite material is a CN materialImportant is the method of modification.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a composite photocatalyst, and a preparation method and an application thereof, aiming at the defects of the prior art. The invention comprises graphite-phase carbon nitride and tin oxide composite barium sulfate (SnO)2/BaSO4etch，SBOetch) The composite photocatalyst of the electron transport material can efficiently catalyze and degrade triethanolamine with the catalytic activity of 284 mu mol g-1h-1The photocatalyst is 2.5 times of pure graphite phase carbon nitride, has catalytic activity obviously higher than that of the existing graphite-like phase carbon nitride photocatalyst, has stable activity within 12 hours, can still maintain 85 percent of original activity within 18 hours, and solves the problem of poor stability of the graphite-like phase carbon nitride photocatalyst.
In order to solve the technical problems, the invention adopts the technical scheme that: the composite photocatalyst is characterized by comprising graphite-phase carbon nitride and tin oxide composite barium sulfate, wherein the mass of the tin oxide composite barium sulfate is 1/30-1 times that of the graphite-phase carbon nitride.
The composite photocatalyst is characterized in that the graphite-phase carbon nitride is obtained by roasting a precursor compound, the temperature rise rate of the roasting treatment is 4-5 ℃/min, the roasting temperature is 500-550 ℃, and the precursor compound is powder urea, powder dicyandiamide or powder melamine.
The composite photocatalyst is characterized in that the precursor compound is urea in a powder state.
The composite photocatalyst is characterized in that the preparation method of the tin oxide composite barium sulfate comprises the following steps:
step one, sequentially adding citric acid monohydrate, barium chloride and stannic chloride into a hydrogen peroxide solution to obtain a precursor solution, dropwise adding ammonia water into the precursor solution until the pH value of the system is 9-11, carrying out heat preservation reaction for 0.5-3 h under the water bath condition of 50-70 ℃, cooling, washing, drying, grinding and roasting to obtain barium stannate;
and step two, putting the barium stannate into deionized water, dropwise adding concentrated sulfuric acid, keeping the temperature for 1-24 h under the water bath condition of 20-80 ℃, washing and drying to obtain the tin oxide composite barium sulfate.
The composite photocatalyst is characterized in that the calcination temperature in the step one is 300-700 ℃.
The composite photocatalyst is characterized in that the mass ratio of barium chloride to tin chloride is 1: 1; and step two, the volume of the concentrated sulfuric acid is 1/300-1/100 of the mass of the barium stannate, the unit of the volume of the concentrated sulfuric acid is mL, and the unit of the mass of the barium stannate is mg.
The composite photocatalyst is characterized in that the water bath temperature in the second step is 35 ℃, and the water bath time is 1 h.
In addition, the invention also provides a method for preparing the composite photocatalyst, which is characterized by comprising the step of carrying out solvothermal reaction on the graphite-phase carbon nitride and tin oxide composite barium sulfate to obtain the composite photocatalyst.
The method is characterized in that the solvent of the solvothermal reaction is absolute ethyl alcohol, and the temperature of the solvothermal reaction is 160-200 ℃; the solvent thermal reaction is carried out in a polytetrafluoroethylene hydrothermal kettle lining sleeved with a stainless steel outer lining.
Furthermore, the invention also provides an application of the composite photocatalyst in photocatalytic degradation of organic pollutants.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a graphite-like phase carbon nitride composite photocatalyst taking graphite-phase carbon nitride and tin oxide composite barium sulfate as main components, and the catalytic activity of the composite catalyst reaches 284 mu mol g in the process of catalyzing and degrading triethanolamine- 1h-1The photocatalyst is 2.5 times of untreated graphite-phase carbon nitride, the photocatalytic activity is stable within 12 hours, 85 percent of the original activity can be still maintained within 18 hours, and the problems of low catalytic activity and poor stability of the existing graphite-like carbon nitride photocatalyst are effectively solved.
2. The present invention provides aThe method for preparing the composite catalyst by solvothermal reaction can obtain the composite barium sulfate (CN/SBO) of stably combined graphite phase carbon nitride and tin oxideetch) The formed composite catalyst makes full use of the electron transmission performance of the tin oxide composite barium sulfate material, promotes the separation of graphite phase carbon nitride photon-generated carriers, and improves the activity of degrading organic wastewater.
3. The preparation process is simple and easy to popularize and apply.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Drawings
FIG. 1(a) shows CN in example 1-1 and SBO in example 2-1etchAnd CN/SBO of examples 3-1 to 3-5etch-x(x is 0, 10, 30, 100, 300, respectively) and FIG. 1(b) is SBO of example 2-1etchXRD pattern of (A) and BaSO4Pdf standard card of (1).
FIG. 2(a) shows CN in example 1-1 and SBO in example 2-1etchAnd CN/SBO of examples 3-1 to 3-5etchFTIR spectrum (400-4000 cm) of-x (x is 0, 10, 30, 100, 300, respectively)-1) And (b) is the FTIR spectrum (400-2000 cm) of each sample-1)。
FIG. 3(a-h) shows CN, CN/SBOetch-0、CN/SBOetch-3、CN/SBOetch-10、 CN/SBOetch-30、CN/SBOetch-100、CN/SBOetch300 and SBOetchSEM image of (1 μm).
FIG. 4(a) CN/SBOetch-0、CN/SBOetch-100 and SBOetch(ii) XPS full scan, (b) CN/SBOetch-0、CN/SBOetch-100 and SBOetchHigh resolution O1s spectrum of (c) CN/SBOetchAnd CN/SBOetch Ba 3d high resolution spectrum of-100, (d) CN/SBOetch-100 and SBOetchHigh resolution spectrum of Sn 3 d.
FIG. 5(a-d) shows CN, CN/SBOetch-0、CN/SBOetch-100 and SBOetchTEM image of (e, f) CN/SBOetchHRTEM of 100.
FIG. 6(a) is CN/SBOetch-100, and (b) is SBOetchEDS mapping map of (a).
FIG. 7 shows CN, CN/SBOetch-0、CN/SBOetch-100 and SBOetchThe isothermal adsorption-desorption curve (a) and the pore volume-pore diameter map (b).
FIG. 8(a) shows CN, CN/SBOetch-x and SBOetchThe UV-Vis plot of (a) and (b) are Tauc plot.
FIG. 9(a) is CN/SBOetch-0 and SBOetchM-S curve of (b) is CN and SBOetch(c) is CN/SBOetch-0 and SBOetchXPS VB spectrum of (d) is CN/SBOetch-0、CN/SBOetch-100 and SBOetchEIS curve of (1).
FIG. 10(a) shows CN, CN/SBOetch-0 and CN/SBOetchA steady state PL spectrum of-100, and (b) a transient PL spectrum.
FIG. 11(a) shows CN-melamine, CN and CN/SBOetchTEOA degradation Activity for 5h for samples of the x series, (b) CN/SBOetchAverage TEOA degrading Activity per hour for the x series of samples, (c) CN/SBOetch-100 photocatalytic degradation TEOA activity stability test.
FIG. 12 is CN/SBOetchTEM image (a) after recovery of 100 Pt-loaded photocatalytic degradation TEOA, (b-c) HRTEM image, and (d) EDS mapping image.
FIG. 13 is CN/SBOetchThe visible light of the catalyst catalyzes and degrades TEOA and generates hydrogen simultaneously.
Detailed Description
The invention provides a composite photocatalyst which comprises graphite-phase carbon nitride and tin oxide composite barium sulfate, wherein the mass of the tin oxide composite barium sulfate is 1/30-1 times that of the graphite-phase carbon nitride. The mass of the tin oxide composite barium sulfate is 1/30, 1/10, 1/3 or 1 time of that of the graphite-phase carbon nitride; the composite photocatalyst is formed by compounding graphite-phase carbon nitride and tin oxide composite barium sulfate, and in the photocatalysis process, the tin oxide composite barium sulfate is used for promoting the photoproduction electron migration of the graphite-phase carbon nitride and simultaneously enabling photoproduction charges to be separated in space and inhibit the two from being compounded, so that the CN photocatalysis degradation of organic matters is realized.
Further, the graphite-phase carbon nitride is obtained by roasting a precursor compound, the heating rate of the roasting treatment is 4 ℃/min to 5 ℃/min, the roasting temperature is 500 ℃ to 550 ℃, the precursor compound is powder urea, powder dicyandiamide or powder melamine, the heating rate of the roasting treatment can be 4 ℃/min or 5 ℃/min, and the roasting temperature can be 500 ℃, 525 ℃ or 550 ℃.
Further, the tin oxide composite barium sulfate in the invention is prepared by the following method:
step one, sequentially adding citric acid monohydrate, barium chloride and stannic chloride into a hydrogen peroxide solution to obtain a precursor solution, dropwise adding ammonia water into the precursor solution until the pH value of the system is 9-11, carrying out heat preservation reaction for 0.5-3 h under the water bath condition of 50-70 ℃, cooling, washing, drying, grinding and roasting to obtain barium stannate; the pH value in the first step can be 9, 10 or 11, the water bath condition can be 50 ℃, 60 ℃ or 70 ℃, and the heat preservation time can be 0.5h, 1h or 3 h;
step two, putting the barium stannate into deionized water, dropwise adding concentrated sulfuric acid, keeping the temperature for 1-24 h under the water bath condition of 20-80 ℃, washing and drying to obtain tin oxide composite barium sulfate; the temperature of the water bath in the second step can be 20 ℃, 35 ℃ or 80 ℃, and the heat preservation time can be 1h, 4h or 24 h;
furthermore, the roasting temperature in the first step is 300-700 ℃, for example, the roasting temperature can be 300 ℃, 550 ℃ or 700 ℃;
further, the mass ratio of the barium chloride to the tin chloride is 1: 1; the volume of the concentrated sulfuric acid in the second step is 1/300-1/100 of the mass of the barium stannate, the unit of the volume of the concentrated sulfuric acid is mL, and the unit of the mass of the barium stannate is mg; the volume of the concentrated sulfuric acid is 1/300, 3/500 or 1/100 based on the mass of barium stannate;
further, the composite photocatalyst is prepared by the following method: carrying out solvothermal reaction on graphite-phase carbon nitride and tin oxide composite barium sulfate to obtain a composite photocatalyst, wherein the solvent of the solvothermal reaction is absolute ethyl alcohol, and the temperature of the solvothermal reaction is 160-200 ℃; the solvothermal reaction is carried out in a polytetrafluoroethylene hydrothermal kettle lining sleeved with a stainless steel outer lining; the temperature of the solvothermal reaction may be 160 ℃, 180 ℃ or 200 ℃.
The present invention will be described in detail with reference to the following examples, which are not intended to limit the present invention.
A series of composite photocatalysts are prepared by the method disclosed by the invention, and the method is as follows.
Examples 1 to 1
The embodiment provides a preparation method of graphite-phase carbon nitride, which comprises the following steps:
step one, grinding 20g of urea into powder, and putting the powder into a 50mL ceramic crucible;
step two, placing the ceramic crucible filled with the urea powder in a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and preserving heat for 4 hours;
and step three, naturally cooling the system after heat preservation in the step two to room temperature, and grinding the system into powder in an agate mortar to obtain graphite-phase Carbon Nitride (CN).
Examples 1 to 2
The embodiment provides a preparation method of graphite-phase carbon nitride, which comprises the following steps:
step one, grinding 1g of melamine into powder, and putting the powder into a 25mL ceramic crucible;
step two, placing the ceramic crucible filled with the melamine powder in a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and preserving heat for 4 hours;
and step three, naturally cooling the system after heat preservation in the step two to room temperature, and grinding the system into powder in an agate mortar to obtain the graphite-phase carbon nitride.
Examples 1 to 3
The embodiment provides a preparation method of graphite-phase carbon nitride, which comprises the following steps:
step one, grinding 3g of dicyandiamide into powder, and putting the powder into a 50mL ceramic crucible;
placing the ceramic crucible filled with dicyandiamide powder in an ash furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours;
and step three, naturally cooling the system after heat preservation in the step two to room temperature, and grinding the system into powder in an agate mortar to obtain the graphite-phase carbon nitride.
Examples 1 to 4
The embodiment provides a preparation method of graphite-phase carbon nitride, which comprises the following steps:
step one, grinding 20g of urea into powder, and putting the powder into a 50mL ceramic crucible;
step two, placing the ceramic crucible filled with the urea powder in a muffle furnace, heating to 500 ℃ at the heating rate of 4 ℃/min, and preserving heat for 4 hours;
and step three, naturally cooling the system after heat preservation in the step two to room temperature, and grinding the system into powder in an agate mortar to obtain the graphite-phase carbon nitride.
Examples 1 to 5
The embodiment provides a preparation method of graphite-phase carbon nitride, which comprises the following steps:
step one, grinding 20g of urea into powder, and putting the powder into a 50mL ceramic crucible;
step two, placing the ceramic crucible filled with the urea powder in a muffle furnace, raising the temperature to 550 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 1 h;
and step three, naturally cooling the system after heat preservation in the step two to room temperature, and grinding the system into powder in an agate mortar to obtain the graphite-phase carbon nitride.
Example 2-1
The embodiment provides a preparation method of tin oxide composite barium sulfate, which comprises the following steps:
step one, adding 5mmol of citric acid monohydrate into 170mL of hydrogen peroxide solution with the mass percentage of 30%, and stirring until the solution is colorless and transparent to obtain the hydrogen peroxide solution containing the citric acid monohydrate;
step two, adding 10mmol of barium chloride into the hydrogen peroxide solution containing citric acid monohydrate in the step one, stirring until the barium chloride is completely dissolved, adding 10mmol of tin chloride, and stirring until the tin chloride is completely dissolved to obtain a precursor solution;
step three, dropwise adding ammonia water into the precursor solution obtained in the step two until the pH value of the system is 10, and stopping dropwise adding; the mass percentage content of the ammonia water is 26%;
step four, transferring the system after ammonia water is dripped in the step three to a 50 ℃ water bath kettle, and carrying out heat preservation and stirring reaction for 1 h;
step five, cooling the system after heat preservation in the step four to room temperature, washing and centrifuging the solid phase by deionized water until the supernatant is neutral, drying the washed solid phase in a 60 ℃ oven for 8h, grinding, putting 1g of ground powder in a 25mL ceramic crucible, putting the ceramic crucible filled with the ground powder in a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, preserving heat, firing for 1h, stopping heating, and naturally cooling to obtain white powdery barium stannate; the washing centrifugation is carried out in a centrifuge;
step six, mixing the barium stannate BaSnO in the step five3Putting 300mg into a beaker with the volume of 250mL and containing 167mL of deionized water, and stirring for 5 minutes;
step seven, dropwise adding 3mL of concentrated sulfuric acid, and then transferring the beaker to a preheated 35 ℃ water bath kettle for heat preservation for 1 h; the concentrated sulfuric acid with the mass percentage of 98% is preferably selected;
step eight, centrifugally washing the system subjected to water bath heat preservation in the step seven by using deionized water for 3 times, and then drying the system in a 60-DEG C oven for 8 hours to obtain white powder which is tin oxide composite barium sulfate and is named as SnO2/BaSO4etchSBO for shortetch。
Examples 2 to 2
The embodiment provides a preparation method of tin oxide composite barium sulfate, which comprises the following steps:
step one, adding 5mmol of citric acid monohydrate into 170mL of hydrogen peroxide solution with the mass percentage of 30%, and stirring until the solution is colorless and transparent to obtain the hydrogen peroxide solution containing the citric acid monohydrate;
step two, adding 10mmol of barium chloride into the hydrogen peroxide solution containing citric acid monohydrate in the step one, stirring until the barium chloride is completely dissolved, adding 10mmol of tin chloride, and stirring until the tin chloride is completely dissolved to obtain a precursor solution;
step three, dropwise adding ammonia water into the precursor solution obtained in the step two until the pH value of the system is 9, and stopping dropwise adding; the mass percentage content of the ammonia water is 28%;
step four, transferring the system after ammonia water is dripped in the step three to a water bath kettle at the temperature of 60 ℃, and carrying out heat preservation, stirring and reaction for 0.5 h;
step five, cooling the system after heat preservation in the step four to room temperature, washing and centrifuging the solid phase by deionized water until the supernatant is neutral, drying the washed solid phase in a 60 ℃ oven for 8h, grinding, putting 1g of ground powder in a 25mL ceramic crucible, putting the ceramic crucible filled with the ground powder in a muffle furnace, heating to 300 ℃ at a heating rate of 5 ℃/min, preserving heat, firing for 1h, stopping heating, and naturally cooling to obtain white powdery barium stannate;
step six, mixing the barium stannate BaSnO in the step five3Putting 300mg into a beaker with the volume of 250mL and containing 167mL of deionized water, and stirring for 5 minutes;
step seven, dropwise adding 1mL of concentrated sulfuric acid, and then transferring the beaker to a preheated 35 ℃ water bath kettle for heat preservation for 1 h;
step eight, centrifugally washing the system subjected to water bath heat preservation in the step seven for 3 times by using deionized water, and then drying the system in a drying oven at the temperature of 60 ℃ for 8 hours to obtain white powder which is tin oxide composite barium sulfate.
Examples 2 to 3
The embodiment provides a preparation method of tin oxide composite barium sulfate, which comprises the following steps:
step one, adding 5mmol of citric acid monohydrate into 170mL of hydrogen peroxide solution with the mass percentage of 30%, and stirring until the solution is colorless and transparent to obtain the hydrogen peroxide solution containing the citric acid monohydrate;
step two, adding 10mmol of barium chloride into the hydrogen peroxide solution containing citric acid monohydrate in the step one, stirring until the barium chloride is completely dissolved, adding 10mmol of tin chloride, and stirring until the tin chloride is completely dissolved to obtain a precursor solution;
step three, dropwise adding ammonia water into the precursor solution obtained in the step two until the pH value of the system is 11, and stopping dropwise adding; the mass percentage content of the ammonia water is 25%;
step four, transferring the system after ammonia water is dripped in the step three to a water bath kettle at 70 ℃, and carrying out heat preservation and stirring reaction for 3 hours;
step five, cooling the system after heat preservation in the step four to room temperature, washing and centrifuging the solid phase by deionized water until the supernatant is neutral, drying the washed solid phase in a 60 ℃ oven for 8h, grinding, putting 1g of ground powder in a 25mL ceramic crucible, putting the ceramic crucible filled with the ground powder in a muffle furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat, firing for 1h, stopping heating, and naturally cooling to obtain white powdery barium stannate; the washing is carried out in a centrifuge;
step six, mixing the barium stannate BaSnO in the step five3Putting 500mg into a beaker with the volume of 250mL and containing 167mL of deionized water, and stirring for 5 minutes;
step seven, dropwise adding 3mL of concentrated sulfuric acid, and then transferring the beaker to a preheated 35 ℃ water bath kettle for heat preservation for 1 h;
step eight, centrifugally washing the system subjected to water bath heat preservation in the step seven for 3 times by using deionized water, and then drying the system in a drying oven at the temperature of 60 ℃ for 8 hours to obtain white powder which is tin oxide composite barium sulfate.
Examples 2 to 4
The embodiment provides a preparation method of tin oxide composite barium sulfate, which comprises the following steps:
step one, adding 5mmol of citric acid monohydrate into 170mL of hydrogen peroxide solution with the mass percentage of 30%, and stirring until the solution is colorless and transparent to obtain the hydrogen peroxide solution containing the citric acid monohydrate;
step two, adding 10mmol of barium chloride into the hydrogen peroxide solution containing citric acid monohydrate in the step one, stirring until the barium chloride is completely dissolved, adding 10mmol of tin chloride, and stirring until the tin chloride is completely dissolved to obtain a precursor solution;
step three, dropwise adding ammonia water into the precursor solution obtained in the step two until the pH value of the system is 11, and stopping dropwise adding; the mass percentage content of the ammonia water is 25%;
step four, transferring the system after ammonia water is dripped in the step three to a water bath kettle at 70 ℃, and carrying out heat preservation and stirring reaction for 3 hours;
step five, cooling the system after heat preservation in the step four to room temperature, washing and centrifuging the solid phase by deionized water until the supernatant is neutral, drying the washed solid phase in a 60 ℃ oven for 8h, grinding, putting 1g of ground powder in a 25mL ceramic crucible, putting the ceramic crucible filled with the ground powder in a muffle furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat, firing for 1h, stopping heating, and naturally cooling to obtain white powdery barium stannate; the washing is carried out in a centrifuge;
step six, mixing the barium stannate BaSnO in the step five3Putting 500mg into a beaker with the volume of 250mL and containing 167mL of deionized water, and stirring for 5 minutes;
step seven, dropwise adding 3mL of concentrated sulfuric acid, and then transferring the beaker to a preheated water bath kettle at the temperature of 20 ℃ for heat preservation for 24 hours;
step eight, centrifugally washing the system subjected to water bath heat preservation in the step seven for 3 times by using deionized water, and then drying the system in a drying oven at the temperature of 60 ℃ for 8 hours to obtain white powder which is tin oxide composite barium sulfate.
Examples 2 to 5
The embodiment provides a preparation method of tin oxide composite barium sulfate, which comprises the following steps:
step one, adding 5mmol of citric acid monohydrate into 170mL of hydrogen peroxide solution with the mass percentage of 30%, and stirring until the solution is colorless and transparent to obtain the hydrogen peroxide solution containing the citric acid monohydrate;
step two, adding 10mmol of barium chloride into the hydrogen peroxide solution containing citric acid monohydrate in the step one, stirring until the barium chloride is completely dissolved, adding 10mmol of tin chloride, and stirring until the tin chloride is completely dissolved to obtain a precursor solution;
step three, dropwise adding ammonia water into the precursor solution obtained in the step two until the pH value of the system is 11, and stopping dropwise adding; the mass percentage content of the ammonia water is 25%;
step four, transferring the system after ammonia water is dripped in the step three to a water bath kettle at 70 ℃, and carrying out heat preservation and stirring reaction for 3 hours;
step five, cooling the system after heat preservation in the step four to room temperature, washing and centrifuging the solid phase by deionized water until the supernatant is neutral, drying the washed solid phase in a 60 ℃ oven for 8h, grinding, putting 1g of ground powder in a 25mL ceramic crucible, putting the ceramic crucible filled with the ground powder in a muffle furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat, firing for 1h, stopping heating, and naturally cooling to obtain white powdery barium stannate; the washing is carried out in a centrifuge;
step six, mixing the barium stannate BaSnO in the step five3Putting 500mg into a beaker with the volume of 250mL and containing 167mL of deionized water, and stirring for 5 minutes;
step seven, dropwise adding 3mL of concentrated sulfuric acid, and then transferring the beaker to a preheated water bath kettle at the temperature of 80 ℃ for heat preservation for 4 hours;
step eight, centrifugally washing the system subjected to water bath heat preservation in the step seven for 3 times by using deionized water, and then drying the system in a drying oven at the temperature of 60 ℃ for 8 hours to obtain white powder which is tin oxide composite barium sulfate.
Example 3-1
This example provides a composite photocatalyst comprising the graphite-phase carbon nitride of example 1-1 and the tin oxide composite barium Sulfate (SBO) of example 2-1etch) Said SBOetchThe mass is 1/3 times of the mass of the graphite phase carbon nitride.
The embodiment also provides a preparation method of the composite photocatalyst, which includes:
step one, take 300mg of the graphite phase carbon nitride of example 1-1 and 100mg of the SBO of example 3-1etchAdding the mixture into a polytetrafluoroethylene hydrothermal kettle lining with the volume of 100mL, then adding 20mL of ethanol, and carrying out ultrasonic treatment for 20min to obtain a suspension;
step two, placing the inner liner filled with the suspension in the step one into a stainless steel hydrothermal kettle shell, preserving heat in a preheated oven at 180 ℃ for carrying out solvothermal reaction for 24 hours, centrifugally washing the reacted system with deionized water for 3 times, and then placing the system into an oven at 60 ℃ for drying for 8 hours to obtain faint yellow powder as the composite photocatalyst; the rotation speed of each centrifugal washing is 10000rpm, the time of each centrifugal washing is 3min, and the name is CN/SBOetch-100(100Is SBOetchThe amount of charge) of the reactor.
Examples 3 to 2
This example provides a composite photocatalyst comprising the graphite-phase carbon nitride of example 1-1 and the tin oxide composite barium Sulfate (SBO) of example 2-1etch) Said SBOetchThe mass is 1 time of the mass of the graphite phase carbon nitride.
The embodiment also provides a preparation method of the composite photocatalyst, which includes:
step one, take 300mg of the graphite phase carbon nitride of example 1-1 and 300mg of the SBO of example 3-1etchAdding the mixture into a polytetrafluoroethylene hydrothermal kettle lining with the volume of 100mL, then adding 20mL of ethanol, and carrying out ultrasonic treatment for 20min to obtain a suspension;
step two, placing the inner liner filled with the suspension in the step one into a stainless steel hydrothermal kettle shell, preserving heat in a preheated oven at 180 ℃ for carrying out solvothermal reaction for 24 hours, centrifugally washing the reacted system with deionized water for 3 times, and then placing the system into an oven at 60 ℃ for drying for 8 hours to obtain faint yellow powder as the composite photocatalyst; the rotation speed of each centrifugal washing is 10000rpm, the time of each centrifugal washing is 3min, and the name is CN/SBOetch-300。
Examples 3 to 3
This example provides a composite photocatalyst comprising the graphite-phase carbon nitride of example 1-1 and the tin oxide composite barium Sulfate (SBO) of example 2-1etch) Said SBOetchThe mass is 0.1 times of the mass of the graphite phase carbon nitride.
The embodiment also provides a preparation method of the composite photocatalyst, which includes:
step one, take 300mg of the graphite phase carbon nitride of example 1-1 and 30mg of the SBO of example 3-1etchAdding the mixture into a polytetrafluoroethylene hydrothermal kettle lining with the volume of 100mL, then adding 20mL of ethanol, and carrying out ultrasonic treatment for 20min to obtain a suspension;
step two, placing the inner lining filled with the suspension liquid in the step one into a stainless steel hydrothermal kettle shell, preserving heat in a preheated oven at 180 ℃ for 24 hours of solvothermal reaction, and using deionized water to react the reacted systemCentrifugally washing for 3 times, and drying in an oven at 60 ℃ for 8 hours to obtain light yellow powder as the composite photocatalyst; the rotation speed of each centrifugal washing is 10000rpm, the time of each centrifugal washing is 3min, and the name is CN/SBOetch-30。
Examples 3 to 4
This example provides a composite photocatalyst comprising the graphite-phase carbon nitride of example 1-1 and the tin oxide composite barium Sulfate (SBO) of example 2-1etch) Said SBOetchThe mass is 1/30 of the mass of graphite phase carbon nitride.
The embodiment also provides a preparation method of the composite photocatalyst, which includes:
step one, take 300mg of the graphite phase carbon nitride of example 1-1 and 10mg of the SBO of example 3-1etchAdding the mixture into a polytetrafluoroethylene hydrothermal kettle lining with the volume of 100mL, then adding 20mL of ethanol, and carrying out ultrasonic treatment for 20min to obtain a suspension;
step two, placing the inner liner filled with the suspension in the step one into a stainless steel hydrothermal kettle shell, preserving heat in a preheated oven at 180 ℃ for carrying out solvothermal reaction for 24 hours, centrifugally washing the reacted system with deionized water for 3 times, and then placing the system into an oven at 60 ℃ for drying for 8 hours to obtain faint yellow powder as the composite photocatalyst; the rotation speed of each centrifugal washing is 10000rpm, the time of each centrifugal washing is 3min, and the name is CN/SBOetch-10。
Examples 3 to 5
The embodiment provides a method for processing graphite-phase carbon nitride, which comprises the following steps:
step one, adding 300mg of the graphite-phase carbon nitride of the embodiment 1-1 into a lining of a polytetrafluoroethylene hydrothermal kettle with the volume of 100mL, then adding 20mL of ethanol, and carrying out ultrasonic treatment for 20min to obtain a suspension;
step two, placing the inner liner filled with the suspension in the step one into a stainless steel hydrothermal kettle shell, preserving heat in a preheated oven at 180 ℃ for carrying out solvothermal reaction for 24 hours, centrifugally washing the reacted system with deionized water for 3 times, and then placing the system into an oven at 60 ℃ for drying for 8 hours to obtain faint yellow powder as the composite photocatalyst; the rotational speed of each centrifugal washing was 10000rpm, 3min for each centrifugal washing, named CN/SBOetch-0。
Examples 3 to 6
This example provides a composite photocatalyst comprising the graphite-phase carbon nitride of example 1-2 and the tin oxide barium sulfate composite (SBO) of example 2-2etch) Said SBOetchThe mass is 1/30 of the mass of graphite phase carbon nitride.
The embodiment also provides a preparation method of the composite photocatalyst, which includes:
step one, take 300mg of the graphite phase carbon nitride of example 1-1 and 10mg of the SBO of example 3-1etchAdding the mixture into a polytetrafluoroethylene hydrothermal kettle lining with the volume of 100mL, then adding 20mL of ethanol, and carrying out ultrasonic treatment for 20min to obtain a suspension;
step two, placing the inner liner filled with the suspension in the step one into a stainless steel hydrothermal kettle shell, preserving heat in a preheated oven at 160 ℃ for carrying out 28-hour solvothermal reaction, centrifugally washing the reacted system with deionized water for 3 times, and then placing the system into an oven at 60 ℃ for drying for 8 hours to obtain faint yellow powder as the composite photocatalyst; the rotation speed of each centrifugal washing is 10000rpm, and the time of each centrifugal washing is 3 min.
Examples 3 to 7
This example provides a composite photocatalyst comprising the graphite-phase carbon nitride of examples 1-3 and the tin oxide barium sulfate composite (SBO) of examples 2-3etch) Said SBOetchThe mass is 1/30 of the mass of graphite phase carbon nitride.
The embodiment also provides a preparation method of the composite photocatalyst, which includes:
step one, take 300mg of the graphite phase carbon nitride of example 1-1 and 10mg of the SBO of example 3-1etchAdding the mixture into a polytetrafluoroethylene hydrothermal kettle lining with the volume of 100mL, then adding 20mL of ethanol, and carrying out ultrasonic treatment for 20min to obtain a suspension;
step two, placing the inner liner filled with the suspension in the step one into a stainless steel hydrothermal kettle shell, preserving heat in a preheated oven at 200 ℃ for carrying out solvothermal reaction for 18 hours, centrifugally washing the reacted system with deionized water for 3 times, and then placing the system into an oven at 60 ℃ for drying for 8 hours to obtain faint yellow powder as the composite photocatalyst; the rotation speed of each centrifugal washing is 10000rpm, and the time of each centrifugal washing is 3 min.
Performance evaluation:
FIG. 1(a) shows CN in example 1-1 and SBO in example 2-1etchAnd CN/SBO of examples 3-1 to 3-5etchXRD patterns of x (x is 0, 10, 30, 100, 300, respectively), FIG. 1(b) is SBO of example 2-1etchXRD pattern of (A) and BaSO4Pdf standard card of (1).
In FIG. 1a, CN and CN/SBO etch0 two characteristic diffraction peaks at 13.2 ℃ and 27.3 ℃ respectively, respectively assigned to g-C3N4Of (2) and (002), the characteristic peak at 13.2 ℃ is g-C3N4The arrangement of the continuous heptazine ring structure in (1) results, and the characteristic peak at 27.3 DEG is due to the stacking of conjugated aromatic structures, corresponding to g-C3N4Interlayer spacing of the nanoplatelets.
FIG. 1b, SBOetchShowing only BaSO4Characteristic diffraction peaks (JCPDS #01-089-3749) without SnO2May occur due to SnO under acidic conditions2More prone to amorphous structure and so no characteristic peaks appear. By comparison, it can be found that CN/SBOetch-10、 CN/SBOetch-30、CN/SBOetch-100 and CN/SBOetchTwo CN and SBO species were present in each case at-300etchDiffraction peaks of the material, indicating CN and SBOetchSuccessfully compounded and with SBOetchWith increasing addition of (B), the diffraction peak of CN gradually weakens, SBOetchThe characteristic peak of (A) becomes stronger, which indicates that with SBOetchIncreased charge SBO in the sampleetchThe content also increases, which on the other hand also indicates SBOetchHas an inhibiting effect on CN surface structure.
FIG. 2(a) shows CN in example 1-1 and SBO in example 2-1etchAnd CN/SBO of examples 3-1 to 3-5etchFTIR spectrum (400-4000 cm) of-x (x is 0, 10, 30, 100, 300, respectively)-1) And (b) is the FTIR spectrum (400-2000 cm) of each sample-1)。
FIG. 3(a-h) shows CN, CN/SBOetch-0、CN/SBOetch-3、CN/SBOetch-10、CN/SBOetch-30、 CN/SBOetch-100、CN/SBO etch300 and SBOetchSEM image of (1 μm).
In FIG. 2a, the full spectrum shows the dependence on SBO in the sampleetchIncrease in amount, SBOetchGradually appeared, which is consistent with the results of XRD and SEM tests, in fig. 2b, SBOetchShows an infrared spectrum at 562cm-1The spectral band of (A) is caused by Sn-O vibration, which indicates SBOetchIn which SnO is contained2Is located at 610cm-1And 643cm-1The peak of (A) is attributed to SO4 2-Out-of-plane bending vibration of 983cm-1、1076cm-1And 1115cm-1Is classified as SO4 2-Consistent with XRD results. In FIG. 2b, the spectrum of the CN sample is at 1636cm-1、 1414cm-1、1324cm-1、1240cm-1The peak at (B) belongs to the stretching vibration peak of the aromatic C-N heterocyclic ring, 808cm-1The spectrum peak shows the stretching vibration of triazine unit in CN, and the infrared characteristic spectrum peak of CN is basically unchanged compared with the infrared characteristic spectrum peak of the sample after compounding, which shows that the structure of CN before and after compounding is stable and not damaged, and CN/SBOetchThe occurrence of the composite sample obviously belongs to BaSO4Shows CN and SBOetchSuccessful composition of.
FIGS. 3a and b are SEM pictures of CN materials before and after ethanol heating at 180 ℃ (FIGS. 3a1 and 3a2 are CN of example 1, and FIGS. 3b1 and 3b2 are CN/SBOetch-0), the morphology of CN before and after ethanol heating is not obviously changed, and the CN is composed of stacked curled nano-sheets.
FIG. 3c, d, e, f, g are CN/SBO in sequenceetch-3、CN/SBOetch-10、CN/SBOetch-30、 CN/SBOetch-100 and CN/SBOetchSEM image of-300 with SBOetchThe appearance of CN changes with the increase of the feeding amount, and the CN is gradually cracked from a large sheet shape into a smaller sheet shape. When CN and SBOetchWhen the mass of (2) is 1:1, a large amount of SBO appears on CN nano-chips obviouslyetchAnd (3) granules.
FIG. 3h is SBOetchSEM picture of (g), it can be seen that SBO isetchThe smallest nanoparticle size should be below 100nm, and the larger particles in the figure may be due to small particle agglomeration, SBOetchThe particle size of the precursor is consistent with the particle size (20-30 nm) of the precursor BSO, which shows that CN and SBOetchAre successfully combined together.
FIG. 4(a) CN/SBOetch-0、CN/SBOetch-100 and SBOetch(ii) XPS full scan, (b) CN/SBOetch-0、CN/SBOetch-100 and SBOetchHigh resolution O1s spectrum of (c) CN/SBOetchAnd CN/SBOetchBa 3d high resolution spectrum of-100, (d) CN/SBOetch-100 and SBOetchHigh resolution spectrum of Sn 3 d.
As can be seen from the broad scan (FIG. 4a), CN/SBOetchBa, Sn, O, S, N and C in-100, N, O and C in CN/SBOetch-0, SBOetchBa, Sn, S, O and C are contained in-0. This demonstrates CN/SBO etch100 successful complexation of the two substances in the sample.
As can be seen in FIG. 4b, CN/SBOetchCharacteristic peaks in the spectrum of O1s in the-0 sample at 533.0eV and 531.9eV are assigned to oxygen and O-C-N, SBO contained in the adsorbed water, respectivelyetchThe characteristic peaks in the O1s spectrum of the sample at 532.2eV and 530.9eV are assigned to SO4 2-And Sn-O, CN/SBOetchCharacteristic peaks in the spectrum of O1s in the-100 sample at 532.9eV, 532.1eV and 531.1 eV are assigned to oxygen and SO contained in the adsorbed water, respectively4 2-Or O-C-N and Sn-O.
By CN/SBOetchThe Ba 3d spectra of the-100 samples (fig. 4c) revealed a 15.2eV spacing between the two peaks, both spin-splitting peaks of the Ba 3d orbital. By comparing CN/SBOetch-100 and SBOetchThe peak between Ba 3d can be seen as SBOetchThe binding energy was shifted by 1eV toward the direction of high binding energy after binding to CN, probably because Ba was in contact with C and N, which are nonmetallic elements in CN due to C and N electricityAre all more negative than Ba and result in Ba being in a chemical environment that is electron-deprived.
SBOetchIn the Sn 3d spectrum (FIG. 4d) of the sample, two strong peaks at 487.0eV and 495.4eV are assigned to Sn 5/2d and Sn 3/2d, respectively, which indicates that Sn is represented by Sn4+The method of (1) exists. By comparing CN/SBOetch-100 and SBOetchSn 3d peak between and Sn-O corresponding O1s peak, SBOetchAfter the CN is combined, the binding energy is respectively shifted to the low binding energy direction by 0.3eV and 0.2eV, and the shifting of the binding energy to the low direction is probably caused by electron enrichment, which indicates that CN/SBOetchSnO of-1002Some will enrich electrons, and the electrons on CN tend to move to SnO2Migration, which accounts for SBOetchBecoming a new electronic channel on the CN.
FIG. 5(a-d) shows CN, CN/SBOetch-0、CN/SBOetch-100 and SBOetchTEM image of (e, f) CN/SBOetchHRTEM of 100.
FIG. 5a and FIG. 5b are CN and CN/SBO, respectivelyetchTEM picture of-0, it can be seen that CN presents the morphology of thin-layer nanosheet.
FIG. 5d is SBOetchTEM image of (B), SBO can be seenetchIs nano particles of about 20nm and BaSnO3The particle size of (a) is close, indicating that a small size of SBO is successfully obtainedetchAnd (3) granules.
FIG. 5c is CN/SBOetchTEM image of-100, SBOetchThe nano particles are loaded in g-C3N4On the nano-chip, to further confirm the nano-particle component and the combination mode of the two, the nano-chip is used for CN/SBO etch100 HRTEM test, according to FIGS. e and f and measuring the occurrence of nanoparticles with a lattice spacing of 0.332nm belonging to BaSO4(102) Crystal face, it can be confirmed that the nanoparticle bonded to CN is SBOetch。
FIG. 6(a) is CN/SBOetch-100, and (b) is SBOetchEDS mapping chart of
FIG. 6a is CN/SBOetchMapping plot of-100, the darker part is g-C as seen from the element distribution of N3N4The brighter portion can be judged from the distribution of Ba, Sn and OIs SBOetchAnd (4) nanocrystals. From the distribution law, g-C3N4On successfully load SBOetchAnd (4) nanocrystals. FIG. 6b is SBOetchEDS mapping chart of (SBO)etchOnly Ba, Sn, S and O are contained and uniformly distributed. This is consistent with the XPS results, with the nanoparticle component in HRTEM being SBO as described aboveetchAnd (5) the consistency is achieved.
FIG. 7 shows CN, CN/SBOetch-0、CN/SBOetch-100 and SBOetchThe isothermal adsorption-desorption curve (a) and the pore volume-pore diameter map (b).
TABLE 1 CN, CN/SBOetch-0、CN/SBOetch-100 and SBOetchBET specific surface area of (2).
TABLE 1 CN, CN/SBOetch-0、CN/SBOetch-100 and SBOetchBET specific surface area of
FIG. 7a is a graph showing the adsorption and desorption curves of nitrogen, CN and CN/SBOetch-0、CN/SBOetch-100 and SBOetchThe samples all showed a tendency of a lower adsorption amount in the low pressure stage and a significant increase in the nitrogen adsorption amount with an increase in pressure, but the hysteresis loop between the adsorption and desorption curves was not significant, indicating that there were fewer micropores and mesopores therein.
The specific surface areas of the two compounds calculated according to the BET formula are shown in Table 1, CN/SBOetch-0 and CN/SBOetch-100 and SBOetchHas specific surface areas of 50.7, 53.2, 59.3 and 85.0m2 g-1This indicates SBOetchThe original channel structure of CN is not damaged by the introduction of (2), and the slightly increased specific surface area is probably due to SBOetchThe specific surface area itself.
FIG. 7b is a pore diameter-pore volume differential curve with no apparent peaks appearing in the CN sample curve, illustrating pore size irregularity, while CN/SBOetch-0 and CN/SBOetchThe peak at-100 at 20nm indicates that pores with a pore size around 20nm are the largest. CN, CN/SBOetch-0 andCN/SBOetch-100 and SBOetchHave a pore volume of 0.29, 0.30 and 0.13cm, respectively3 g-1The pore diameters are respectively 104.0 nm, 94.2 nm, 91.7 nm and 26.5nm, CN/SBO etch100 samples with CN/SBOetchA similar pore structure curve at-0 also indicates SBOetchWithout destroying the porous structure of the CN itself.
FIG. 8(a) shows CN, CN/SBOetch-x and SBOetchThe UV-Vis plot of (a) and (b) are Tauc plot.
As shown in FIG. 8a, the absorption edge of CN is at-450 nm, corresponding to a band gap width, SBO, of 2.75eVetchThe ultraviolet visible diffuse reflection spectrum shows that the absorption edge is positioned at 325nm, and the absorption edge does not belong to BaSO4Possibly amorphous SnO in the sample2Also laterally demonstrate SBOetchThe material contains SnO2And (3) components. Furthermore, CN/SBOetchHas substantially no change in absorption edge and light absorption capacity compared to CN, which also indicates that SBOetchIs introduced to destroy the structure of CN.
From the Tauc-plot of FIG. 8b, it can be concluded that SBOetchThe introduction of (2) has no obvious influence on the band gap of CN materials, and proves that SBOetchThe introduction of (2) does not affect the good light absorption performance of CN itself.
FIG. 9(a) is CN/SBOetch-0 and SBOetchM-S curve of (b) is CN and SBOetch(c) is CN/SBOetch-0 and SBOetchXPS VB spectrum of (d) is CN/SBOetch-0、CN/SBOetch-100 and SBOetchEIS curve of (1).
By means of the M-S curve, CN/SBOetch-0 and SBOetchThe slope of the tangent line of the longest linear portion of the curve is positive, and accordingly, both are n-type semiconductors, and the CN/SBO can be obtained from the intersection point of the tangent line of the M-S curve and the X axisetch-0 and SBOetchThe flat band potentials of (a) and (b) were 1.31V vs. RHE and 1.10V vs. RHE, respectively.
The difference between the n-type semiconductor flat band potential and the semiconductor CB is generally about 0.2eV, CN/SBOetch-0 and SBOetchThe absolute positions of CB were 1.51eV and 1.31eV, respectively (FIG. 9 a). CN/SBO obtained by combining Tauc-plotetch-0 and SBOetchThe band gap widths of (A) are 2.88 eV and 4.10eV, respectively, and the relationship between the band gap widths and the band gap positions is shown in FIG. 9 b.
To further confirm the belt position relationship, we are dealing with CN/SBOetch-0 and SBOetchThe XPS valence band spectrum test of the sample was performed, and the results are shown in FIG. 9c, and it can be seen from FIG. 9c that CN/SBOetch-0 and SBOetchThe valence band positions of the probe are 2.28eV and 3.65eV respectively, due to the influence of an XPS instrument on the absolute value of VB, the XPS VB absolute position result is greatly different from VB obtained by a Tauc-plot method and an M-S curve method, but under the same test condition of the same XPS instrument, the relative position of the obtained VB result is basically consistent with the relative position of VB under the real condition, in the test, CN/SBO is measured by an XPS VB spectrumetch-0 and SBOetchThe relative difference of the valence bands is 1.37eV, the difference of VB obtained by the Tauc-plot method and the M-S curve method is 1.42eV, and the results of the two methods are basically consistent, which shows that the energy band positions of the two materials are obtained by utilizing the Tauc-plot method and the M-S curve.
To further study SBOetchThe sample was tested for electrochemical impedance with the introduction of an effect on CN charge transfer properties to obtain an EIS impedance spectrum (fig. 9d), which is used to verify the interfacial charge transfer properties of the prepared sample. CN-SBOetchThe smaller radius of the arc of 100 reflects the low resistance effect, which corresponds to a faster electron transfer and separation, favouring the supply of more carriers for the photocatalytic hydrogen production and TEOA degradation reactions. In the composite photocatalyst, CN-SBOetch-0 and CN-SBO etch100 shows larger and smaller arc radii, respectively, indicating CN-SBOetchThe-100 material has less charge transfer resistance, and can promote more effective separation of photo-generated charges, thereby improving the performance of the photocatalyst.
FIG. 10(a) shows CN, CN/SBOetch-0 and CN/SBOetchA steady state PL spectrum of-100, and (b) a transient PL spectrum.
TABLE 2 CN/SBOetch-0 and CN/SBOetch-1A carrier decay lifetime of 00.
TABLE 2 CN/SBOetch-0 and CN/SBOetch-100 carrier decay lifetimes
As shown in FIG. 10a, CN/SBOetch-0 shows a fluorescence emission peak at around-475 nm, CN/SBOetchThe-100 sample showed a stronger fluorescence peak at 475 nm. This process is further understood by time-resolved transient PL spectroscopy, as shown in fig. 10b, where the emission decay data is fitted by bi-exponential kinetics and the intensity decay mean lifetime is derived by the following equation:
the results show that in pure CN/SBOetchIn-0, the average carrier lifetime is 10.73ns, while in CN/SBOetchAverage carrier lifetime of 10.95ns in-100 (Table 2), with longer carrier lifetimes indicating CN and SBOetchThe interfacial charge transfer therebetween suppresses the recombination of photo-induced charge carriers.
FIG. 11(a) shows CN/SBOetchTEOA degradation activity for 5h for the x series of samples, with CN-melamine as the graphitic carbon nitride (CN-melamin) obtained with melamine as precursor in examples 1-2; (b) is CN/SBOetchAverage TEOA degrading Activity per hour for the x series of samples, (c) CN/SBOetch-100 stability test of the activity of photocatalytic degradation of TEOA, reaction conditions: 50mg of catalyst, 0.5mg of Pt, 186mL of 10% TEOA solution. The degradation test method determines the consumption of Triethanolamine (TEOA) according to the generation amount of hydrogen, and calculates the degradation rate of the triethanolamine. The report of Yann Pellegrin et al in 2017 shows that one TEOA molecule loses two electrons in the degradation process, and one hydrogen molecule, namely n, is correspondingly generated according to the conservation of chargeTEOA＝nH2. The application method comprises measuring side irradiation by photocatalysisThe device analyzes and calculates the yield of the photocatalytic reaction gas, and comprises: the device comprises a Pyrex glass reactor with the volume of 240mL, a 300W xenon lamp (model: LF300B-F) provided with a 420nm cut-off filter, a magnetic stirrer and a circulating cooling water system, wherein a gas testing device comprises a high-precision microsyringe (the capacity is 0-500 mu L), a gas chromatograph (high-purity argon is used as a carrier gas, a molecular sieve chromatographic column is of a TDX-01 type, and a heat conduction detector) and a computer system.
The specific operation is as follows:
the method comprises the following steps: mounting a 420nm optical filter on a light outlet of a xenon lamp, starting a power supply of the xenon lamp to preheat for more than 15min, and keeping the current, the voltage and the light intensity of the xenon lamp stable in the test process;
dispersing the sample into a reaction bottle filled with the pollutants containing the triethanolamine substances according to a preset amount, and adding H2PtCl4Purging with Ar for 15min, exhausting impurity gas in the reactor, and taking the condition that no oxygen exists in a gas test as a standard; the pollutants containing the ethanolamine substances are triethanolamine solutions;
step three: the plane of the side illumination of the reaction bottle is opposite to the light outlet of the xenon lamp, a circulating cooling water power supply is turned on to maintain the constant temperature of the reactor, a magnetic stirrer is turned on, the rotating speed is adjusted to be fixed, the photocatalyst is dispersed in the triethanolamine solution, and the TEOA is degraded in a photocatalytic manner while the Pt is carried out in-situ light deposition;
step four: after the reaction starts, sampling the gas in the reactor from the upper silica gel plug by using a microsyringe at intervals of 1h, extracting 200 mu L of gas, injecting the gas into a gas chromatograph, and testing and recording the content of the hydrogen;
and step five, after the test is finished, closing the xenon lamp, the magnetic stirrer and the power supply of the circulating water machine, and cleaning and storing the used reactor.
50mg of sample graphite phase Carbon Nitride (CN) was added to 186mL of 10 vol% TEOA solution, and 0.5mg equivalent of Pt loaded H2PtCl4In the process of carrying out the photo-deposition and platinum-carrying of the solution and simultaneously degrading TEOA, comparing the CN and CN-melamine activities in FIG. 11a, the CN fired by using urea as the precursor has higher activity than that fired by using melamine as the precursorHigh. Comparison of CN and CN/BSOetchThe activity of-0 shows that ethanol heat has no substantial effect on the photocatalytic activity of CN itself. Second, it was found that the activity of the sample was dependent on SBOetchThe material feeding shows the trend of increasing first and then decreasing when the SBO is adoptedetchThe material dosage is 100mg, namely mCN: mSBOetchWhen the catalyst is 300:100, the catalyst activity is highest and reaches 14.2 mu mol h-1Are each CN (6.1. mu. mol h)-1) And CN/SBOetch-0(5.3μmol h-1) 2.5 times and 2.8 times of the sample (fig. 11 b). From fig. 11c it can be seen that the photocatalyst showed no decrease in catalytic activity in two cycles and a 15% decrease in the third cycle, probably due to the overnight soaking of the catalyst in solution for 12 h. The above shows that the catalyst has stable activity within 12h, and can still maintain 85% of the original activity within 18 h.
FIG. 12 is CN/SBOetchTEM image (a) after recovery of 100 Pt-loaded photocatalytic degradation TEOA, (b-c) HRTEM image, and (d) EDS mapping image. Wherein CN/SBOetch-100 Pt supported CN/SBO by in-situ photo-deposition as described in FIG. 11etch-100 Pt loading.
To verify SBOetchLoaded at g-C3N4The function of the electron channel is shown in the above, we are on CN/SBOetchTEM and EDS mapping of samples recovered after degrading TEOA with 100 Pt loadings, it can be seen from FIG. 12a that the recovered samples are derived from SBO of nanoparticlesetchg-C of nanosheets3N4And Pt nanoparticles. As can be seen in FIGS. 12b and 12C, g-C3N4And SBOetchThere are photo-deposited Pt nanoparticles on both, but Pt nanoparticles are more prone to deposit on SBOetchThe above.
FIG. 12d is an EDS mapping chart of the recovered sample from which N, Ba and Pt elements identify CN and SBO, respectivelyetchAnd position of Pt it can be seen that photo-deposited Pt atoms are more prone to deposit on SBOetchThe above. In the course of the reaction H2PtCl6Would tend to be reduced to elemental particles of Pt at the surface active sites where the photo-generated electrons migrate, indicating that the photo-generated electrons would flow from CN to SBOetch. It was found in the present invention that Pt tends to depositIn SBOetchIndicates SBOetchWith reducing conditions of SBOetchLoaded at g-C3N4Exist as electron channels, promote g-C3N4The separation of photogenerated carriers.
FIG. 13 is CN/SBOetchThe visible light of the catalyst catalyzes and degrades TEOA and generates hydrogen simultaneously.
The invention CN/SBOetchThe mechanism of the photocatalyst may be: thermal ethanol process to SBOetchSuccessfully loaded on a CN nano-chip to form a heterojunction, and when CN is excited by visible light, the generated photo-generated electrons are rapidly transferred to SBOetchThe nanoparticles in turn react with water to form H2The holes oxidize the TEOA molecules in the solution. SBOetchOn one hand, the photo-generated electron migration on CN is promoted, on the other hand, the photo-generated charges are separated in space and inhibited from being compounded, and therefore the activity of visible light catalytic degradation TEOA of CN is improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The composite photocatalyst is characterized by comprising graphite-phase carbon nitride and tin oxide composite barium sulfate, wherein the mass of the tin oxide composite barium sulfate is 1/30-1 times that of the graphite-phase carbon nitride.
2. The composite photocatalyst of claim 1, wherein the graphite-phase carbon nitride is obtained by roasting a precursor compound, the temperature rise rate of the roasting treatment is 4-5 ℃/min, the roasting temperature is 500-550 ℃, and the precursor compound is powdered urea, powdered dicyandiamide or powdered melamine.
3. The composite photocatalyst of claim 2, wherein the precursor compound is urea in powder form.
4. The composite photocatalyst as claimed in claim 1, wherein the preparation method of the tin oxide composite barium sulfate comprises:
step one, sequentially adding citric acid monohydrate, barium chloride and stannic chloride into a hydrogen peroxide solution to obtain a precursor solution, dropwise adding ammonia water into the precursor solution until the pH value of the system is 9-11, carrying out heat preservation reaction for 0.5-3 h under the water bath condition of 50-70 ℃, cooling, washing, drying, grinding and roasting to obtain barium stannate;
and step two, putting the barium stannate into deionized water, dropwise adding concentrated sulfuric acid, keeping the temperature for 1-24 h under the water bath condition of 20-80 ℃, washing and drying to obtain the tin oxide composite barium sulfate.
5. The composite photocatalyst of claim 4, wherein the calcination temperature in the first step is 300 ℃ to 700 ℃.
6. The composite photocatalyst as claimed in claim 4, wherein the mass ratio of barium chloride to tin chloride is 1: 1; and step two, the volume of the concentrated sulfuric acid is 1/300-1/100 of the mass of the barium stannate, the unit of the volume of the concentrated sulfuric acid is mL, and the unit of the mass of the barium stannate is mg.
7. The composite photocatalyst of claim 4, wherein the temperature of the water bath in the second step is 35 ℃ and the time of the water bath is 1 h.
8. A method for preparing the composite photocatalyst of claim 1, comprising subjecting the graphite phase carbon nitride and tin oxide composite barium sulfate to solvothermal reaction to obtain the composite photocatalyst.
9. The method according to claim 8, wherein the solvent of the solvothermal reaction is absolute ethanol, and the temperature of the solvothermal reaction is 160-200 ℃; the solvent thermal reaction is carried out in a polytetrafluoroethylene hydrothermal kettle lining sleeved with a stainless steel outer lining.
10. Use of the composite photocatalyst of claim 1 in photocatalytic degradation of organic pollutants.
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